Report No. 9B TEREPHTHALIC ACID AND DIMETHYL TEREPHTHALATE SUPPLEMENT B by LLOYD M. ELKIN With contributions by Shigeyoshi Takaoka Kohsuke Ohta September 1970 e A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA e I CONTENTS 1 INTRODUCTION . 1 2 SUMMARY........................... 3 3 INDUSTRY STATUS . 13 4 CHEMISTRY......................... 23 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst . 23 Bis(2-hydroxyethyl) Terephthalate from Ethylene Oxide and Terephthalic Acid . , . , . 25 Ammoxidation of p-Xylene . 26 dlycolysis of Terephthalonitrile . 28 Terephthalic Acid by Bromine-Promoted Catalytic Oxidation of p-Xylene ., . 30 Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator . 32 Terephthalic Acid by Nitric Acid Oxidation of p-Xylene . 32 Terephthalic Acid from Phthalic Anhydride . 33 5 REVIEW OF PATENTS . , . 37 Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene . , . 37 Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Activators . 38 Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications . , . 39 Terephthalic Acid by Nitric Acid Oxidation of p-Xylene . 40 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst . , . 40 Terephthalic Acid from p-Xylene by Other Oxidation Processes . , . , 42 Terephthalic Acid from Phthalic Anhydride or Benzoic Acid . 42 Terephthalonitrile, Preparation and Purification . 42 Dimethyl Terephthalate by Esterification of Terephthalic Acid.......................... 43 Bis(2-hydroxyethyl) Terephthalate from Terephthalic Acid and Ethylene Oxide or from Terephthalonitrile . 44 Purification of Terephthalic Acid . 44 Miscellaneous . 45 CONTENTS 6 TEREPHTHALIC ACID FROM p-XYLENE BY LIQUID PHASE OXIDATION IN THE PRESENCE OF LARGE AMOUNTS OF CATALYST , , . 97 Introduction ....................... 97 Process Description .................... 98 Process Discussion .................... 109 Cost Estimates ...................... 111 Capital Costs ...................... 111 Production Costs .................... 112 7 PURE BIS(2-HYDROXYETHYL) TEREPHTHALATE FROM ETHYLENE OXIDE AND CRUDE TEREPHTHALIC ACID . , . , . 119 Introduction ....................... 119 Process Description .................... 119 Process Discussion .................... 129 Source of Crude Terephthalic Acid ............ 129 Recovery of Unreacted Ethylene Oxide .......... 129 Recovery of Triethylamine ................ 129 Mixer and Settler Residence Times ............ 130 Recycle of Crude Bis(2-hydroxyethyl) Terephthalate ... 130 Cost Estimates ...................... 130 Capital Costs ...................... 130 Production Costs .................... 131 8 PURIFICATION OF TEREPHTHALIC ACID BY SUBLIMATION ..... 135 Introduction ....................... 135 Process Description .................... 137 Process Discussion .................... 143 Cost Estimates ...................... 143 Capital Costs ...................... 143 Production Costs .................... 144 Cost Comparison ..................... 144 vi - CONTENTS APPENDIX A DESIGN AND COST BASIS . , . 149 APPENDIX B PHYSICAL DATA ................... 155 APPENDIX C PRODUCT SPECIFICATIONS ............... 157 CITED REFERENCES ........................ 159 SUPPLEMENTARY REFERENCES . 183 CITED REFERENCES FOR SUPPLEMENT A TO PEP REPORT NO. 9 . 197 PATENT REFERENCES BY COMPANY . 199 vii ILLUSTRATIONS 6.1 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Product Yield Versus Reaction Time . , . , . , . 99 6.2 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst , . 103 6.3 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Effect of Operating Level and Plant Capacity on Production Cost . 117 7.1 Pure Bis(2-hydroxyethyl) Terephthalate from Ethylene Oxide and Crude Terephthalic Acid . , . , , , . , . , 123 8.1 Purity of Final Product as a Function of the Mol Ratio of Steam to Terephthalic Acid . , . 136 8.2 Purification of Terephthalic Acid by Sublimation . 139 B.l Solubility of Terephthalic Acid in Glacial Acetic Acid and Aqueous Acetic Acid as a Function Temperature . , . 156 ix TABLES 2.1 Terephthalic Acid Manufacture Summary of Capital and Production Costs . 5 3.1 Dimethyl Terephthalate and Terephthalic Acid Plant Capacities in the Americas . , . , . 15 3.2 Dimethyl Terephthalate and Terephthalic Acid Plant Capacities in Western Europe and the Middle East . 17 3.3 Dimethyl Terephthalate and Terephthalic Acid Plant Capacities in the Far East . , . 19 3.4 Dimethyl Terephthalate and Terephthalic Acid Plant Capacities in the Iron Curtain Countries . , . 21 5.1 Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene Patent Summary . , . 46 5.2 Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Activators Patent Summary . ..'........... 47 5.3 Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Patent Summary . , . , . 48 5.4 Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Patent Summary . , . , . 49 5.5 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Patent Summary . 50 5.6 Terephthalic Acid from p-Xylene by Other Oxidation Processes Patent Summary . , . , . 51 5.7 Terephthalic Acid from Phthalic Anhydride or Benzoic Acid Patent Summary . , . .. 53 5.8 Terephthalonitrile, Preparation and Purification Patent Summary . 59 xi TABLES 5.9 Terephthalonitrile from p-Xylene by Ammoxidation Patent Summary . , . , , . , . , . 67 5.10 Dimethyl Terephthalate by Esterification of Terephthalic Acid Patent Summary . , , . , . 69 5.11 Dimethyl Terephthalate from Terephthalic Acid Reactor Conditions and Yields Patent Summary . , . 73 5.12 Bis(2-hydroxyethyl) Terephthalate from Terephthalic Acid and Ethylene Oxide or from Terephthalonitrile Patent Summary . 75 5.13 Bis(2-hydroxyethyl) Terephthalate from Terephthalic Acid and Ethylene Oxide Patent Summary . 83 5.14 Purification of Terephthalic Acid Patent Summary . , . , . 87 5.15 Miscellaneous Patent Summary , . , . , . 95 6.1 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Major Process Equipment and Utilities Summary . , 103 6.2 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Stream Flows . 107 6.3 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Total Capital Investment . , . 113 6.4 Terephthalic Acid from p-Xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst Production Costs . , . 115 7.1 Pure Bis(2-hydroxyethyl) Terephthalate from Ethylene Oxide and Crude Terephthalic Acid Major Process Equipment and Utilities Summary , . 123 7.2 Pure Bis(2-hydroxyethyl) Terephthalate from Ethylene Oxide and Crude Terephthalic Acid Stream Flows . , . , . 127 xii TABLES 7.3 Pure Bis(2-hydroxyethyl)Terephthalate from Ethylene Oxide and Crude Terephthalic Acid Total Capital Investment . 132 7.4 Pure Bis(2-hydroxyethyl) Terephthalate from Ethylene Oxide and Crude Terephthalic Acid Production Costs . 133 7.5 Pure Bis(2-hydroxyethyl) Terephthalate from Ethylene Glycol and Pure Terephthalic Acid Production Costs (Rough Estimate) . 134 8.1 Purification of Terephthalic Acid by Sublimation Major Process Equipment and Utilities Summary . 139 8.2 Purification of Terephthalic Acid by Sublimation Stream Flows . , . 141 8.3 Purification of Terephthalic Acid by Sublimation Capital Investment . , . , . 145 8.4 Purification of Terephthalic Acid by Sublimation a Production Costs . 146 8.5 Purification of Terephthalic Acid by Sublimation and by Hydrogenation and Crystallization Comparison of Costs . , . , . 147 xiii .